US3450621A - Chlorine cell with flexible elastomeric cover - Google Patents

Chlorine cell with flexible elastomeric cover Download PDF

Info

Publication number
US3450621A
US3450621A US595776A US3450621DA US3450621A US 3450621 A US3450621 A US 3450621A US 595776 A US595776 A US 595776A US 3450621D A US3450621D A US 3450621DA US 3450621 A US3450621 A US 3450621A
Authority
US
United States
Prior art keywords
cover
cell
layer
scale
flexible
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US595776A
Inventor
Ralph F Anderson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Goodrich Corp
Original Assignee
BF Goodrich Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BF Goodrich Corp filed Critical BF Goodrich Corp
Application granted granted Critical
Publication of US3450621A publication Critical patent/US3450621A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/033Liquid electrodes
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/30Cells comprising movable electrodes, e.g. rotary electrodes; Assemblies of constructional parts thereof
    • C25B9/303Cells comprising movable electrodes, e.g. rotary electrodes; Assemblies of constructional parts thereof comprising horizontal-type liquid electrode
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70Assemblies comprising two or more cells

Definitions

  • This invention relates to a cover for a free chlorine generating cell and, in particular, relates to a flexible rubber cover for a De-Nora type chlorine generating cell.
  • This type of cell uses an electrolytic process for producing free chlorine gas from sodium chloride.
  • carbon electrodes are employed for the anode and a pool of mercury is the cathode.
  • the carbon anodes enter the tank by passing vertically through the cover and are adjustably mounted to permit maintenance of a constant electrolytic gap.
  • the chlorine gas is evolved at the anodes and hence it is necessary to provide a seal between the anodes and the cover to prevent the gas from escaping except through the discharge opening.
  • the cover must, therefore, not only seal around the adjustable anodic electrodes but also at the periphery of the tank. "It must also remain flexible to permit electrode adjustment.
  • the De-Nora type cell operates continuously with an electrolyte temperature in the order of 180 to 190 F. Therefore, the flexible cover is subjected to the continuous corrosive attack of hot chlorine gas on the surface thereof disposed on the inside of the tank. In addition, a high concentration of ozone is present in the region around the anodic electrodes on the outside surface of the cover. This subjects the flexible rubber cover to two different corrosive media simultaneously on opposite sides. Previously this environment has caused early failure of the covers by deterioration from heat and corrosive attack.
  • the present invention remedies the above-mentioned difliculties of prior De-Nora type cell covers by providing an improved flexible cover of elastomeric material characterized by having different compositions on the inner and outer surfaces, thereby affording improved resistance of the outer surface to ozone and improved resistance of the inner surface to corrosive attack of hot chlorine gas, as well as improved the capability of the inner surface 3,450,621 Patented June 17, 1969 ice to retain electrolytic salt scale and thereby further protect the cover from corrosion.
  • FIG. 1 is a partial side -view in elevation showing the preferred embodiment of the invention installed in a De-Nora chlorine generating apparatus;
  • FIG. 2 is a transverse sectional view taken along the section-indicating lines 22;
  • FIG. 2a is an enlarged cross sectional view of the cover taken from within the circle 2a of FIG. 2.
  • the De-Nora cell is illustrated as including a tank 10 having a flat horizontal rim flange 10a around the periphery of the open top.
  • the cell is shown as partially filled with brine electrolyte 11 overlying the cathodic electrode 12 which consists of a thin layer of mercury covering the bottom of the tank.
  • the several adjustable spaced anodic electrodes are made of cylindrical carbon blocks 13 suspended from overhead rigid supporting structure 14, here shown as a plate reinforced with I-beams which is independently supported by vertical pillars 15 spaced uniformly around the electrolyte tank.
  • the carbon anodes are secured vertically in an adjustable manner by mechanical fastening means, preferably threaded shafts and lock nuts, to facilitate maintaining a constant gap between the lower ends of the anode and the mercury cathode.
  • the cell has a flexible cover 20 which is sealed around the flange 10a of the tank by being compressed intermediate the clamping frame 21 and the flange 10a.
  • External securing means preferably machine bolts and nuts with the bolts passing through matching holes in the frame, cover and flange are employed to compress the cover between the frame and the flange.
  • the cover is also provided with holes for the anodes to pass therethrough in the illustrated embodiment.
  • the anodes have a threaded portion extending through the last-mentioned holes with sealing between each anode and the flexible cover being effected by the locknuts on the threaded portions tightened sufficiently to clamp the cover between the said nuts and the integral shoulders on the anodes.
  • the improved flexible cover is shown in its presently preferred embodiment in the form of a unitary sheet of layers of different elastomeric material integrally united by being vulcanized together.
  • the upward or outside layer 200 is of uniform thickness and is'made of ethylenepropylene terpolymer material having trans-1,4 hexadiene as the third monomer.
  • the downward or inside layer 20c is also of uniform thickness and is made of a natural rubber composition.
  • a thin tie-gum layer 20b, made of chlorinated butyl rubber, is disposed between the inner and outer layers to facilitate bonding these together by vulcanization.
  • the composite cover has a thickness in the range of 0.125 to 0.200 inch, with the outer layer having a thickness of at least 0.060 inch and a durometer hardness of 60 to 70 on the Shore A scale.
  • the inner layer has a minimum thickness of 0.050 inch and a durometer hardness of 65 to on the Shore A scale.
  • the intermediate tie layer ranges from 0.020 to 0.040 inch in thickness and has a durometer hardness of 50 to 60 on the Shore A scale.
  • the improved cell cover has exhibited a much longer trouble-free life with fewer difficulties in cell operation, such as contamination, than has heretofore been possible with prior cell covers.
  • the longer life is due to the fact that the ethylene-propylene terpolymer rubber exhibits significantly improved resistance to concentrated high temperature ozone which is present in the vicinity of the electrodes on the outer surface of the cover while the natural rubber on the underside of the cover has high resistance to deterioration by the hot chlorine gas in contact with the surface of the cover, although it has a poorer resistance to deterioration by ozone than the ethylene-propylene terpolymer.
  • the capacity of the natural rubber to retain the salt scale from the brine is superior to the scale-retaining capacity of the ethylenepropylene terpolymer so that a protective coating for reducing chlorine attack can be established when the inner surface of the cover is natural rubber.
  • the ethylene-propylene terpolymer comprising the outer surface of the improved cover may be any of the elastomers presently available under that designation.
  • the inner layer can be not only tree-grown natural rubber but also synthesized natural rubber and hence the latter term is used in the generic sense to include both types. Also, while one specific tie-gum has been mentioned in the description for the layer 20b, it will be apparent that other tie-gum compositions can be utilized or the layer 20b can not entirely be omitted if the inner and outer layers are satisfactorily united as an integral sheet.
  • a free chlorine gas generating cell of the De-Nora type having a flexible elastomeric cover comprising an integral sheet with the upward outer face formed of a layer of ethylene-propylene terpolymer material which is resistant to high concentration of ozone, and the downward inner face formed of a layer of natural rubber material which is resistant to hot chlorine gas.
  • said inner layer has a minimum thickness of 0.050 inch and a durometer hardness in the range of 65-75 on the Shore A scale
  • said outer layer has a minimum thickness of 0.060 inch and a durometer hardness of 60-70 on the Shore A scale
  • said cover has a thickness in the range 0.125-0200 inch.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Description

June 17, I969 R. F. ANDERSON 3,450,621
CHLORINE CELL WITH FLEXIBLE ELASTOMERIC COVER Fi led Nov. 21, 1966 INVENTOR. RQ LPH F. ANDERSON United States Patent U.S. Cl. 204-219 5 Claims ABSTRACT OF THE DISCLOSURE An improved flexible sheet rubber cover for sealing the electrolyte tank of a De Nora type chlorine generating cell. Rubber materials of different compositions are used for the opposite surfaces of the cover with the inside surface composed of a natural rubber compound and the outside surface composed of an ethylene-propylene terpolymer rubber.
BACKGROUND OF THE INVENTION This invention relates to a cover for a free chlorine generating cell and, in particular, relates to a flexible rubber cover for a De-Nora type chlorine generating cell. This type of cell uses an electrolytic process for producing free chlorine gas from sodium chloride. In such a cell, carbon electrodes are employed for the anode and a pool of mercury is the cathode. The carbon anodes enter the tank by passing vertically through the cover and are adjustably mounted to permit maintenance of a constant electrolytic gap. The chlorine gas is evolved at the anodes and hence it is necessary to provide a seal between the anodes and the cover to prevent the gas from escaping except through the discharge opening. The cover must, therefore, not only seal around the adjustable anodic electrodes but also at the periphery of the tank. "It must also remain flexible to permit electrode adjustment.
The De-Nora type cell operates continuously with an electrolyte temperature in the order of 180 to 190 F. Therefore, the flexible cover is subjected to the continuous corrosive attack of hot chlorine gas on the surface thereof disposed on the inside of the tank. In addition, a high concentration of ozone is present in the region around the anodic electrodes on the outside surface of the cover. This subjects the flexible rubber cover to two different corrosive media simultaneously on opposite sides. Previously this environment has caused early failure of the covers by deterioration from heat and corrosive attack.
During operation of the De-Nora type cell, salt deposits from the brine electrolyte form on the under surface of the cover. These deposits, when present in the form of a continuous scale, serve as a protective coating in preventing further corrosive attack by the chlorine gaS. However, one of the problems encountered in operating the De-Nora type cell has been separation of the scale from the underside of the cover. This results in portions of the scale falling into the brine thereby contaminating the electrolyte as well as exposing the cover to further corrosive attack.
SUMMARY OF THE INVENTION The present invention remedies the above-mentioned difliculties of prior De-Nora type cell covers by providing an improved flexible cover of elastomeric material characterized by having different compositions on the inner and outer surfaces, thereby affording improved resistance of the outer surface to ozone and improved resistance of the inner surface to corrosive attack of hot chlorine gas, as well as improved the capability of the inner surface 3,450,621 Patented June 17, 1969 ice to retain electrolytic salt scale and thereby further protect the cover from corrosion.
These and other novel features of the invention will become apparent from the following description of the presently preferred embodiment and certain modifications thereof described with reference to the accompanying drawings forming a part of the application.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a partial side -view in elevation showing the preferred embodiment of the invention installed in a De-Nora chlorine generating apparatus;
FIG. 2 is a transverse sectional view taken along the section-indicating lines 22; and
FIG. 2a is an enlarged cross sectional view of the cover taken from within the circle 2a of FIG. 2.
. DETAILED DESCRIPTION As shown in the drawings, the De-Nora cell is illustrated as including a tank 10 having a flat horizontal rim flange 10a around the periphery of the open top. The cell is shown as partially filled with brine electrolyte 11 overlying the cathodic electrode 12 which consists of a thin layer of mercury covering the bottom of the tank. The several adjustable spaced anodic electrodes are made of cylindrical carbon blocks 13 suspended from overhead rigid supporting structure 14, here shown as a plate reinforced with I-beams which is independently supported by vertical pillars 15 spaced uniformly around the electrolyte tank. The carbon anodes are secured vertically in an adjustable manner by mechanical fastening means, preferably threaded shafts and lock nuts, to facilitate maintaining a constant gap between the lower ends of the anode and the mercury cathode. The cell has a flexible cover 20 which is sealed around the flange 10a of the tank by being compressed intermediate the clamping frame 21 and the flange 10a. External securing means, preferably machine bolts and nuts with the bolts passing through matching holes in the frame, cover and flange are employed to compress the cover between the frame and the flange. The cover is also provided with holes for the anodes to pass therethrough in the illustrated embodiment. The anodes have a threaded portion extending through the last-mentioned holes with sealing between each anode and the flexible cover being effected by the locknuts on the threaded portions tightened sufficiently to clamp the cover between the said nuts and the integral shoulders on the anodes.
The improved flexible cover is shown in its presently preferred embodiment in the form of a unitary sheet of layers of different elastomeric material integrally united by being vulcanized together. The upward or outside layer 200 is of uniform thickness and is'made of ethylenepropylene terpolymer material having trans-1,4 hexadiene as the third monomer. The downward or inside layer 20c is also of uniform thickness and is made of a natural rubber composition. A thin tie-gum layer 20b, made of chlorinated butyl rubber, is disposed between the inner and outer layers to facilitate bonding these together by vulcanization. Preferably, the composite cover has a thickness in the range of 0.125 to 0.200 inch, with the outer layer having a thickness of at least 0.060 inch and a durometer hardness of 60 to 70 on the Shore A scale. The inner layer has a minimum thickness of 0.050 inch and a durometer hardness of 65 to on the Shore A scale. The intermediate tie layer ranges from 0.020 to 0.040 inch in thickness and has a durometer hardness of 50 to 60 on the Shore A scale.
The improved cell cover has exhibited a much longer trouble-free life with fewer difficulties in cell operation, such as contamination, than has heretofore been possible with prior cell covers. The longer life is due to the fact that the ethylene-propylene terpolymer rubber exhibits significantly improved resistance to concentrated high temperature ozone which is present in the vicinity of the electrodes on the outer surface of the cover while the natural rubber on the underside of the cover has high resistance to deterioration by the hot chlorine gas in contact with the surface of the cover, although it has a poorer resistance to deterioration by ozone than the ethylene-propylene terpolymer. Moreover, the capacity of the natural rubber to retain the salt scale from the brine is superior to the scale-retaining capacity of the ethylenepropylene terpolymer so that a protective coating for reducing chlorine attack can be established when the inner surface of the cover is natural rubber.
The ethylene-propylene terpolymer comprising the outer surface of the improved cover may be any of the elastomers presently available under that designation. The inner layer can be not only tree-grown natural rubber but also synthesized natural rubber and hence the latter term is used in the generic sense to include both types. Also, while one specific tie-gum has been mentioned in the description for the layer 20b, it will be apparent that other tie-gum compositions can be utilized or the layer 20b can not entirely be omitted if the inner and outer layers are satisfactorily united as an integral sheet. These and further modifications and adaptations not expressly disclosed herein may be made without exceeding the ambit of the invention which is limited only as required by the spirit and scope of the appended claims.
I claim:
1. A free chlorine gas generating cell of the De-Nora type having a flexible elastomeric cover comprising an integral sheet with the upward outer face formed of a layer of ethylene-propylene terpolymer material which is resistant to high concentration of ozone, and the downward inner face formed of a layer of natural rubber material which is resistant to hot chlorine gas.
2. The invention as defined in claim 1 wherein a layer of chlorinated butyl rubber is intermediate said inner and said outer layers.
3. The invention as defined in claim 1 wherein said inner layer has a minimum thickness of 0.050 inch and a durometer hardness in the range of 65-75 on the Shore A scale, said outer layer has a minimum thickness of 0.060 inch and a durometer hardness of 60-70 on the Shore A scale, and said cover has a thickness in the range 0.125-0200 inch.
4. The invention as defined in claim 3 wherein the said intermediate layer has a thickness in the range 0.020- 0.040 inch and a durometer hardness of 50-60 on the Shore A scale.
5. The invention defined in claim 1, wherein the ethylene-propylene terpolymer contains trans-1,4 hexadiene as the third monomer.
References Cited UNITED STATES PATENTS 2,958,635 11/1960 De Nora 204-279 2,998,374 8/1961 Granfors 204279 ALLEN B. CURTIS, Primary Examiner.
D. L. WALTON, Assistant Examiner.
US. Cl. X.R. 204279
US595776A 1966-11-21 1966-11-21 Chlorine cell with flexible elastomeric cover Expired - Lifetime US3450621A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US59577666A 1966-11-21 1966-11-21

Publications (1)

Publication Number Publication Date
US3450621A true US3450621A (en) 1969-06-17

Family

ID=24384634

Family Applications (1)

Application Number Title Priority Date Filing Date
US595776A Expired - Lifetime US3450621A (en) 1966-11-21 1966-11-21 Chlorine cell with flexible elastomeric cover

Country Status (2)

Country Link
US (1) US3450621A (en)
DE (1) DE1667526A1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4087343A (en) * 1977-02-23 1978-05-02 The Goodyear Tire & Rubber Company Flexible cover of a platy-filled composition for an electrolytic cell
US4100053A (en) * 1977-12-07 1978-07-11 The B. F. Goodrich Company Flexible cover for a chlorine cell
US4283263A (en) * 1979-03-06 1981-08-11 Industrie Pirelli S.P.A. Cover for electrolytic cells
US4344633A (en) * 1981-05-22 1982-08-17 Diamond Shamrock Corporation Gasket for electrolytic cell
US4585527A (en) * 1984-02-03 1986-04-29 Imperial Chemical Industries Plc Electrolytic cell
US6200437B1 (en) 1997-01-10 2001-03-13 Bayer Aktiengesellschaft Wall-covering for electrolytic cells

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2958635A (en) * 1957-12-24 1960-11-01 Oronzio De Nora Impianti Electrolytic cell cover
US2998374A (en) * 1959-02-09 1961-08-29 Goodyear Tire & Rubber Container linings

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2958635A (en) * 1957-12-24 1960-11-01 Oronzio De Nora Impianti Electrolytic cell cover
US2998374A (en) * 1959-02-09 1961-08-29 Goodyear Tire & Rubber Container linings

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4087343A (en) * 1977-02-23 1978-05-02 The Goodyear Tire & Rubber Company Flexible cover of a platy-filled composition for an electrolytic cell
US4100053A (en) * 1977-12-07 1978-07-11 The B. F. Goodrich Company Flexible cover for a chlorine cell
US4283263A (en) * 1979-03-06 1981-08-11 Industrie Pirelli S.P.A. Cover for electrolytic cells
US4344633A (en) * 1981-05-22 1982-08-17 Diamond Shamrock Corporation Gasket for electrolytic cell
US4585527A (en) * 1984-02-03 1986-04-29 Imperial Chemical Industries Plc Electrolytic cell
US6200437B1 (en) 1997-01-10 2001-03-13 Bayer Aktiengesellschaft Wall-covering for electrolytic cells

Also Published As

Publication number Publication date
DE1667526A1 (en) 1971-06-16

Similar Documents

Publication Publication Date Title
US4107023A (en) Filter press halate cell
US3450621A (en) Chlorine cell with flexible elastomeric cover
US4219394A (en) Membrane assembly for electrolytic cells
US4100053A (en) Flexible cover for a chlorine cell
US3318792A (en) Mercury cathode cell with noble metaltitanium anode as cover means
US3898149A (en) Electrolytic diaphragm cell
US4417970A (en) Electrolytic cell for ion exchange membrane method
US4698143A (en) Structural frame for an electrochemical cell
US2542989A (en) Electrolytic cell
US2958635A (en) Electrolytic cell cover
US2334354A (en) Mercury cathode cell
US4886586A (en) Combination electrolysis cell seal member and membrane tentering means for a filter press type electrolytic cell
US2542990A (en) Electrolytic cell
US3140991A (en) Mercury cathode electrolytic cells
US4064031A (en) Electrolyzer
US4028209A (en) Electrolysis cell
NO137946B (en) ELECTROLYTICAL CELL OF THE DIAPHRAGA TYPE FOR CHLORINE ALKALI ELECTROLYSE
US4426270A (en) Monopolar filter-press electrolyzer
CA1160987A (en) Finger type electrolytic cell for the electrolysis of an aqueous alkali metal chloride solution
US3790465A (en) Electrolytic cell including vertical hollow anodes with deflector panels diverging upwardly from each anode
CA1095854A (en) Electyrolytic cell liner and seal device
US3445373A (en) Mercury cathode electrolysis cell
GB1345254A (en) Electrolytic cell
US4013536A (en) Electrolytic cell
US3672973A (en) Cell cover with weakened areas to relieve explosions